Lithium metal oxide electrodes for lithium batteries

ABSTRACT

An uncycled preconditioned electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula Li (2+2x)/(2+x) M′ 2x/(2+x) M (2−2x)/(2+x) O 2−δ , in which 0≦x&lt;1 and δ is less than 0.2, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M′ is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn, and an uncycled electrode of the formula xLi 2 M′O 3 .(1−x)LiMO 2 , in which 0≦x&lt;1, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more first-row transition metals or lighter metal elements in the periodic table, and M′ is one or more ions with an average tetravalent oxidation state selected from the first- and second-row transition metal elements and Sn, the electrode being preconditioned in a proton-containing medium with a pH&lt;7.0. Methods of preconditioning the electrodes are disclosed as are electrochemical cells and batteries containing the electrodes.

RELATED APPLICATIONS

This application is a continuation-in-part of co-pending applicationSer. No. 10/825,931 filed Apr. 15, 2004 which application claimspriority based on application Ser. No. 60/465,034 filed Apr. 24, 2003.

CONTRACTUAL ORIGIN OF THE INVENTION

The United States Government has rights in this invention pursuant toContract No. W-31-109-ENG-38 between the U.S. Department of Energy andThe University of Chicago representing Argonne National Laboratory.

FIELD OF THE INVENTION

This invention relates to improved lithium-metal-oxide positiveelectrodes for lithium cells and batteries, preferably rechargeablelithium-ion cells and batteries. These batteries are used to power awide range of applications such as portable telecommunicationsequipment, computers, medical devices, electric vehicles andhybrid-electric vehicles. More specifically, the invention relates tolithium-metal-oxide electrodes with layered-type structures that arechemically preconditioned prior to cell assembly to improve thecapacity, cycling efficiency and stability of lithium cells andbatteries when charged to high potentials.

BACKGROUND OF THE INVENTION

State-of-the-art lithium-ion cells have a lithiated carbon negativeelectrode, or anode, (Li_(x)C₆) and a lithium-cobalt-oxide positiveelectrode, or cathode, Li_(1−x)CoO₂. During charge and discharge of thecells, lithium ions are transported between the two host structures ofthe anode and cathode with the simultaneous oxidation or reduction ofthe host electrodes, respectively. When graphite is used as the anode,the voltage of the cell is approximately 4 V. The LiCoO₂ cathode, whichhas a layered structure, is expensive and becomes unstable at lowlithium content, i.e., when cells reach an overcharged state at x≧0.5.Alternative, less expensive electrode materials that are isostructuralwith LiCoO₂, such as LiNi_(0.08)Co_(0.2)O₂LiNi_(0.5)Mn_(0.5)O₂ andLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ are being developed with the hope ofreplacing at least part of the cobalt component of the electrode.However, all these layered structures, when extensively delithiatedbecome unstable, because of the high oxygen activity at the surface ofthe particles. Therefore, the delithiated electrode particles tend toreact with the organic solvents of the electrolyte or lose oxygen. Suchreactions at the surface of layered lithium metal oxide electrodes aredetrimental to the performance of the lithium cells and batteries, andmethods are required to combat these reactions to ensure that maximumcapacity and cycle life can be obtained from the cells.

Considerable efforts have already been made in the past to overcome thestability and solubility problems associated with layered LiCoO₂ andLiNiO₂ electrodes. For example, considerable success has been achievedin the past by stabilizing these electrodes by pre-treating theelectrode powders with oxide additives such as Al₂O₃ or ZrO₂ obtainedfrom metal alkoxide precursors such as solutions containing aluminumethylhexanoate diisopropoxide (Al(OOC₈H₁₅)(OC₃H₇)₂ or zirconiumethylhexanoisopropoxide (Zr[(OOC₈H₁₅)₂(OCH₃H₇)₂]) as described, forexample, by J. Cho et al in Chemistry of Materials, Volume 12, page 3788(2000) and J. Cho et al in Electrochemical and Solid State Letters,Volume 4 No. 10, page A159 (2001), respectively, or a zirconium oxide,polymeric precursor or zirconium oxynitrate (ZrO(NO₃)₂.xH₂O) asdescribed by Z. Chen et al in Electrochemical and Solid State Letters,Volume 5, No. 10, page A213 (2002), prior to the fabrication of thefinal electrode thereby making the surface of the LiCoO₂ particles moreresistant to electrolyte attack, cobalt dissolution or oxygen losseffects.

The loss of oxygen from lithium metal oxide electrodes, such as layeredLiCoO₂ and LiNi_(1−y)Co_(y)O₂ electrodes can contribute to exothermicreactions with the electrolyte and with the lithiated carbon negativeelectrode, and subsequently to thermal runaway if the temperature of thecell reaches a critical value. Although some success has been achievedin the past to improve the performance of lithium-ion cells by coatingelectrode particles, the coatings can themselves impede lithiumdiffusion in and out of the layered electrode structure duringelectrochemical discharge and charge. Further improvements in thecomposition of layered lithium-metal oxide electrodes, particularly atthe surface of the electrodes, and in methods to manufacture them arestill required to improve the overall performance and safety of lithiumcells.

SUMMARY OF THE INVENTION

This invention relates to improved lithium-metal-oxide positiveelectrodes for lithium cells and batteries, preferably rechargeablelithium-ion cells and batteries. More specifically, it relates tolayered lithium-metal-oxide electrodes, represented by the generalformula xLi₂M′O₃.(1−x)LiMO₂ (0≦x<1) in which M′ is one or morenon-lithium metal ions with an average tetravalent oxidation state andin which M is two or more non-lithium metal ions with an averagetrivalent oxidation state that are chemically preconditioned prior tocell assembly either by reduction or by acid treatment, or a combinationthereof, to improve the capacity, cycling efficiency and cyclingstability of lithium cells and batteries when charged to highpotentials. The invention extends to methods for synthesizing thepreconditioned lithium-metal-oxide electrodes.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention consists of certain novel features and a combination ofparts hereinafter fully described, illustrated in the accompanyingdrawings, and particularly pointed out in the appended claims, it beingunderstood that various changes in the details may be made withoutdeparting from the spirit, or sacrificing any of the advantages of thepresent invention.

FIG. 1 illustrates the powder X-ray diffraction patterns of a) anuntreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode; b) aLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode treated with NH₃ at 250° C.;and c) a LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode treated with NH₃ at350° C.;

FIG. 2 illustrates the electrochemical voltage profiles, at the 15^(th)cycle, of lithium cells, operated at room temperature (RT) between 4.6and 2.0 V, with a) an untreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂electrode; and b) a NH₃-treated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂electrode;

FIG. 3 illustrates the electrochemical voltage profiles, at the 15^(th)cycle, of lithium cells operated at 50° C. between 4.6 and 2.0 V, witha) an untreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode; and b) aNH₃-treated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode;

FIG. 4 illustrates plots of electrode capacity vs. cycle number oflithium cells, operated at room temperature (RT) between 4.45 and 2.5 V,with a) an untreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode; and b) aNH₃-treated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode;

FIG. 5 illustrates plots of electrode capacity vs. cycle number oflithium cells, operated at room temperature (RT) between 4.6 and 2.0 V,with a) an untreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode; and b) aNH₃-treated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode;

FIG. 6 illustrates plots of electrode capacity vs. cycle number oflithium cells, operated at 50° C. between 4.6 and 2.0 V, with a) anuntreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode; and b) aNH₃-treated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode;

FIG. 7 a illustrates cyclic voltammograms between 4.6 and 2.0 V vs.metallic lithium of an untreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂electrode;

FIG. 7 b illustrates cyclic voltammograms between 4.6 and 2.0 V vs.metallic lithium of a LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode treatedwith NH₃ at 250° C.;

FIG. 7 c illustrates cyclic voltammograms between 4.6 and 2.0 V vs.metallic lithium of a LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode treatedwith NH₃ at 350° C.,

FIG. 8 illustrates the powder X-ray diffraction pattern of a) a0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ composite electrode; b) a0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ composite electrode treated with NH₃at 200° C.; c) a 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ composite electrodetreated first with H₂O at room temperature and then with NH₃ at 200° C.;and d) a 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ composite electrode treatedfirst with HNO₃ at room temperature and then with NH₃ at 200° C.;

FIG. 9 a illustrates the first charge and discharge voltage profiles ofa lithium cell, operated at room temperature, with a0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ composite electrode;

FIG. 9 b illustrates the first charge and discharge voltage profiles ofa lithium cell, operated at room temperature, with a0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ composite electrode treated with NH₃;

FIG. 9 c illustrates the first charge and discharge voltage profiles ofa lithium cell, operated at room temperature, with a0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ composite electrode treated with H₂Oand NH₃;

FIG. 9 d illustrates the first charge and discharge voltage profiles ofa lithium cell, operated at room temperature, with a0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.05)O₂ composite electrode treated withHNO₃ and NH₃;

FIG. 10 a illustrates a plot of electrode capacity vs. cycle number of alithium cell, operated at room temperature between 4.6 and 2.0 V, withan untreated 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ composite electrode;

FIG. 10 b illustrates a plot of electrode capacity vs. cycle number of alithium cell, operated at room temperature between 4.6 and 2.0 V, with a0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.05)O₂ composite electrode treated withNH₃;

FIG. 10 c illustrates a plot of electrode capacity vs. cycle number of alithium cell, operated at room temperature between 4.6 and 2.0 V, with a0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ composite electrode treated with H₂Oand NH₃;

FIG. 10 d illustrates a plot of electrode capacity vs. cycle number of alithium cell, operated at room temperature between 4.6 and 2.0 V, with a0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.05)O₂ composite electrode treated withHNO₃ and NH₃;

FIG. 11 illustrates a schematic representation of an electrochemicalcell; and

FIG. 12 illustrates a schematic representation of a battery consistingof a plurality of cells connected electrically in series and inparallel.

FIG. 13 illustrates the powder X-ray diffraction patterns of:

a) an untreated 0.1 Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂electrode (Sample H);

b) a 0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode treatedwith an acidic 0.014M NH₄F (aqueous) solution and dried at 300° C. inair (Sample I);

c) a 0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode treatedwith an acidic 0.014M NH4F (aqueous) solution and dried at 600° C. inair (Sample J);

d) a 0.1 Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode treatedwith a 0.016M NH₄F solution in methanol and dried at 600° C. in air(Sample K).

FIG. 14 illustrates the first charge and discharge voltage profiles oflithium cells, operated at room temperature, with a) an untreated1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode (Sample H); b)a 0.1 Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode treatedwith an acidic NH₄F solution (aqueous) and dried at 300° C. (Sample I);c) a 0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode treatedwith an acidic NH₄F solution (aqueous) and dried at 600° C. (Sample J);and d) a 0.1 Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrodetreated with a 0.016M NH₄F solution in methanol and dried at 600° C. inair (Sample K).

FIG. 15 illustrates plots of electrode capacity vs. cycle number of alithium cell, operated at room temperature between 4.6 and 3.0 V with anuntreated 1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode (O),(Sample H); a 0.1Li₂MnO₃.0.9LiCo_(0.0372)Ni_(0.372)

_(0.256)O electrode treated with an acidic (aqueous) and dried at300°C.(□), (Sample I); a0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O_(2 electrode treated with an acidic NH)₄F solution (aqueous) and dried at 600° C., (●) (Sample J); and a0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode treated witha 0.016M NH₄F solution (aquesous) and dried at 600° C., (●) (sample J);and a 0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode treatedwith a 0.016M Nh₄F solution in methanol and dried at 600° C. in air, (▪)(Sample K).

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

It is now well known that state-of-the-art LiMO₂ electrodes with layeredstructures such as LiCoO₂, LiNi_(0.08)Co_(0.2)O₂,LiAl_(0.05)Ni_(0.80)Co_(0.15)O₂, LiNi_(0.5)Mn_(0.5)O₂,LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂, LiNi_(0.80)Co_(0.15)Al_(0.05)O₂ andLiCo_(0.90)Ti_(0.05)Mg_(0.05)O₂ electrodes, or variations thereof, forexample, those that contain lithium within the transition metal (M)layers are unstable in a lithium cell environment when a large amount oflithium is extracted from their structures, typically when x exceeds 0.5in Li_(1−x)MO₂ electrodes, or at a potential higher than approximately4.2 V vs. metallic lithium. The high reactivity of the delithiatedelectrode structure has been attributed to the highly oxidizing power ofthe tetravalent metal ions Ni⁴⁺, Co⁴⁺ and Mn⁴⁺, that decreases in theorder Ni⁴⁺>Co⁴⁺>Mn⁴⁺. Highly delithiated Li_(1−x)MO₂ electrodes cantherefore react spontaneously with the organic-based electrolytesolvents such as ethylene carbonate, diethyl carbonate or dimethylcarbonate or, in extreme cases, the Li_(1−x)MO₂ electrode can releaseoxygen into the cell compartment. The oxidation of electrolyte solventsor the release of oxygen from the delithiated electrodes, which can berepresented generically by the formula Li_(1−x)MO_(2−δ) (0<δ<1), must ofnecessity lower the oxidation state of the transition metal ions in theLi_(1−x)MO_(2−δ) product, at least at the surface of the electrodeparticles. Such a reaction takes place predominantly during the initialcharge of a C₆/LiMO₂ lithium-ion cell, when lithium is electrochemicallyextracted from the LiMO₂ positive electrode and inserted into thenegative C₆ (graphite) electrode. These reactions decrease thetheoretical capacity of the LiMO₂ electrode; therefore, these electrodestend to show an enhanced capacity loss on the initial charge/dischargecycle of the lithium-ion cell.

For layered LiMO₂ electrodes that contain Ni, such as LiNiO₂,LiNi_(0.08)Co_(0.2)O₂ and LiAl₀₀₅Ni_(0.80)Co_(0.15)O₂, it has beenobserved that the electrochemically induced capacity loss can beattributed not only to oxygen loss or reaction with the electrolyte, butalso to the migration of the nickel ions into the lithium layer of thedelithiated Li_(1−x)MO_(2−δ) electrode structure. When nickel diffusionoccurs concomitantly with oxygen loss, then the surface of aLi_(1−X)MO_(2−δ) electrode can have characteristic features, forexample, of a Li_(1−x)MO_(2−δ) rocksalt-like structure. For example,lithium extraction and oxygen loss from a Li_(1−x)NiO_(2−δ) electrodeleaves a surface product that closely resembles a Li_(z)Ni_(1−z)O phase.Although a Li_(z)Ni_(1−z)O structure lowers the lithium-ion conductivityat the electrode surface, which can result in an increase in cellimpedance, the reduced surface layer serves to protect the Li_(1−x)MO₂structure within the bulk of the particles during the extended cyclingof the lithium-ion cell. The applicants have found that it isadvantageous to pre-reduce chemically the surface of LiMO₂ electrodeparticles, particularly those containing a slight excess of lithiumwithin the M layers, with a convenient reducing agent to yield aLiMO_(2−δ) electrode product prior to cell assembly so that the extentof oxygen loss from the electrode and the concomitant loss of capacitycould be minimized during the electrochemical charge and discharge ofthe cell. In this respect, the use of reducing environments tosynthesize electrode products has already been disclosed in theliterature for different types of electrodes as discussed by M. M.Thackeray et al in U.S. Pat. No. 5,240,794; in these instances thereduced metal ions exist in the bulk of the electrode structures as wellas at the surface of the particles.

Layered lithium-metal-oxide structures, Li₂M′O₃, in which the M′ ionsare tetravalent, are also known to exist. These structures can bereformulated in standard layered notation as Li[M′_(0.67)Li_(0.33)]O₂ inwhich layers of lithium ions alternate with layers containing both M′-and lithium ions in a 2:1 ratio. One well known example is Li₂MnO₃(Li[Mn_(0.67)Li_(0.33)]O₂) which is electrochemically inactive withrespect to lithium insertion and extraction. However, Li₂MnO₃ can beelectrochemically activated by acid treatment, during which some H⁺—Li⁺ion exchange occurs and some Li₂O may be removed from the structure.

This invention relates, in general, to layered lithium-metal-oxideelectrodes, represented by the general formula xLi₂M′O₃.(1−x)LiMO₂(0≦x<1) in which M′ is one or more non-lithium metal ions with anaverage tetravalent oxidation state and in which M is one or morenon-lithium metal ions with an average trivalent oxidation state thatare chemically preconditioned prior to cell assembly either by reductionor by acid treatment, or a combination thereof, to improve the capacity,cycling efficiency and cycling stability of lithium cells and batterieswhen charged to high potentials. The invention extends to methods forsynthesizing the preconditioned lithium-metal-oxide electrodes. Whenx=0, the formula xLi₂M′O₃.(1−x)LiMO₂ reduces simply to LiMO₂.

Therefore, in a first embodiment, this invention relates to layeredelectrodes represented by the two-component formula xLi₂M′O₃.(1−x)LiMO₂in which 0≦x<1, that can be rewritten alternatively asLi_((2+2x)/(2+x))M′_(2x/(2+x))M_((2−2x)/(2+x))O₂ also for 0≦x<1, inwhich M is a non-lithium metal ion with an average trivalent oxidationstate selected from one or more of the first row transition metals orlighter metal elements in the periodic table, and in which M′ is one ormore ions with an average tetravalent oxidation state selected from thefirst and second row transition metal elements and Sn, the electrodesbeing chemically preconditioned with a reducing agent to yieldLi_((2+2x)/(2+x))M′_(2x/(2+x))M_((2−2x)/(2+x))O_(2−δ) compounds in whichδ is less than 0.2, preferably less than 0.1. The metal ions, M, areselected preferably from Co, Ni, Mn or Ti ions, optionally in thepresence of one or more other cations such as Mg and Al. The M′ cationsare selected from elements that form a Li₂M′O₃ rocksalt-type structurepreferably from Ti, Mn, Zr, Ru and Sn and most preferably from Mn and/orTi that form a layered rocksalt-type structure which is structurallycompatible with the LiMO₂ component. The xLi₂M′O₃.(1−x)LiMO₂ electrodeshave been described previously as having composite electrode structuresby J-S. Kim et al in Electrochemistry Communications, volume 4, page 205(2002). When x=0, the preconditioned electrodes are represented simplyby the formula LiMO_(2−δ).

In a second embodiment of the invention, the xLi₂M′O₃.(1−x)LiMO₂electrodes can be preconditioned by acid treatment optionally followedby the reduction step. When preconditioning occurs by acid treatment,ion-exchange occurs between the H⁺ and Li⁺ ions. In this instance, thepreconditioned xLi₂M′O₃.(1−x)LiMO₂ electrodes can be represented priorto reduction by the general formulaxLi_(2−z)H_(z)O.xM′O₂.(1−x)Li_(1−x)H_(x)MO₂ in which 0’0<z<1, and inwhich the lithium ions are partially ion-exchanged by hydrogen ions. Inaddition, some Li₂O may be removed from the structure during thisprocess. These preconditioned electrodes can be heated, typically totemperatures above 100° C., to remove at least part of the H₂O componentfrom the structure.

Of particular significance to this invention are preconditionedxLi₂M′O₃.(1−x)LiMO₂ electrodes containing a Li₂MnO₃ component (i.e.,M′=Mn). It has already been reported by M. H. Rossouw et al in theJournal of Solid State Chemistry, volume 104, page 464 (1993) thatlithium and oxygen can be removed from Li₂MnO₃ by acid treatment tocreate a composite xLi₂MnO₃.(1−x)MnO₂ structure without destroying thelayered arrangement of the Mn ions; on relithiation, either chemicallywith LiI or electrochemically in an electrochemical cell, lithium can beinserted into the MnO₂ component of the composite structure to yieldxLi₂MnO₃.(1−x)LiMnO₂. These composite electrode structures may containprotons (H⁺ ions) as a result of the H⁺—Li⁺ ion exchange reactions thatoccur, for example, during the preconditioning acid-treatment step orwhen immersed in the non-aqueous electrochemical cells that containacidic electrolytes such as those containing LiPF₆ salts. Forsimplicity, these protons are not always included in the description ofthe preconditioned electrode structures of this invention. Thecomposition of xLi₂MnO₃.(1−x)LiMO₂ electrodes can be modified byselection of one or more appropriate metal (M) cations, preferably fromone or more of Co, Ni, Mn or Ti, ions, optionally in the presence of oneor more other metal cations, selected preferably from the first row oftransition metal elements, or from lighter metal elements in theperiodic table, such as Mg and Al. Examples of such two-componentsystems are xLi₂MnO₃.(1−x)LiCoO₂ as reported by K. Numata et al in SolidState Ionics, volume 118, page 117 (1999), and xLi₂MnO₃.(1−x)LiCrO₂ asreported by B. Ammundsen et al in the Journal of the ElectrochemicalSociety, volume 149, page A431 (2002). Composite electrodes that areshowing particular promise typically contain two or moreelectrochemically-active M cations, for example,Li[Ni_(x)Li_((1/3−2x/3))Mn_((2/3−x/3))]O₂ (0<x<½) as reported by Z. Luet al in Chemistry of Materials, volume 15, page 3214 (2003), which canbe reformulated in composite notation as(1−2x)Li₂MnO₃.(3x)LiMn_(0.5)Ni_(0.5)O₂ for the same range of x, andelectrodes in which M=Co, Mn and Ni, represented generically asxLi₂MnO₃.(1−x)LiCo_(1−a)Ni_(b)Mn_(c)O₂ in which a=b+c.

A major advantage of using two-component xLi₂M′O₃.(1−x)LiMO₂ composite(positive) electrodes, as defined herein, is that the Li₂M′O₃ component,particularly when present as Li₂MnO₃, can be used effectively to supplyan excess of lithium to the positive electrode to offset irreversiblecapacity loss effects associated with the negative electrode oflithium-ion cells, such as lithiated graphite, Li_(x)C₆ (0<x<1). Forexample, it has been established that whenxLi₂MnO₃.(1−x)LiNi_(0.5)Mn_(0.5)O₂ electrodes are charged in lithiumcells, the electrochemical reaction occurs first by lithium extractionfrom the LiNi_(0.5)Mn_(0.5)O₂ component between 3.0 and 4.2 V, andthereafter by a concomitant extraction of lithium from the Li₂MnO₃component. It is believed that the latter process (typically atpotentials between 4.2 and 4.6 V) is also accompanied by the chemicalloss of oxygen from the surface of the delithiatedxLi₂MnO₃.(1−x)LiNi_(0.5)Mn_(0.5)O₂ electrode particles, either as oxygengas or by reaction with the organic solvents of the electrolyte, forexample, organic carbonates such as ethylene carbonate, dimethylcarbonate, diethyl carbonate and the like. In such situations, theresult is not only a chemical reduction of the electrode surface by lossof oxygen, but also the loss of some Li₂O from the Li₂MnO₃ (Li₂O.MnO₂)component that leaves behind an electrochemically active MnO₂ species,thereby increasing the operating capacity of the electrode. Despite thefact that xLi₂M′O₃.(1−x)LiMO₂ composite electrodes exhibit anirreversible capacity loss during the initial cycle, these electrodesprovide significantly higher electrode capacities on subsequent cyclingthan conventional layered LiCoO₂ or LiNiO₂ electrodes and LiMn₂O₄ spinelelectrodes. It would be advantageous to precondition layered LiMO₂ orcomposite xLi₂M′O₃.(1−x)LiMO₂ electrodes chemically prior to assemblingthem in cells by removing oxygen and/or Li₂O from the surface of theelectrodes to minimize irreversible capacity loss effects and toincrease the operating capacity of the electrodes, particularly duringthe early cycling of cells.

According to a third embodiment, the preconditioned electrodes of theinvention can be synthesized by subjecting the parent LiMO₂ or compositexLi₂M′O₃.(1−x)LiMO₂ electrodes, for example, either in powder orlaminate form, to a suitable reducing agent such as ammonia gas, dilutehydrogen gas, for example, 2-6 percent by volume of hydrogen in argongas, carbon monoxide gas, or carbon at moderately high temperatures,such as 150-600° C., to reduce the surface of the LiMO₂ or compositexLi₂M′O₃.(1−x)LiMO₂ electrodes. Gaseous reducing agents, such asammonia, are preferred to solid reducing agents such as finely-dividedcarbon powder because it is easier to control the extent to which thesurface of the LiMO₂ electrode is reduced. Alternatively, the LiMO₂ orcomposite xLi₂M′O₃.(1−x)LiMO₂ electrodes can be reduced by heating theelectrodes under nitrogen gas or air at elevated temperature, typicallyat 600° C. or higher, for example, between 900° C. and 1000° C.simultaneously to remove both oxygen and Li₂O from the surface of theelectrode structure.

In a further embodiment of the invention, the LiMO₂ orxLi₂M′O₃.(1−x)LiMO₂ composite electrodes of the invention canalternatively be subjected, prior to the reduction process describedabove, to a preconditioning step in a proton-containing medium, forexample, de-ionized water or an acidic solution of an inorganic acid oran organic acid with a pH<7.0 such as phosphoric acid, sulfuric acid,nitric acid, acetic acid, hydrochloric acid or the like, for example,hydrofluoric acid, to exchange some of the Li+ ions within the electrodestructure with H⁺ ions, and thereafter to a heating step, preferably forless than 24 hours below 500° C., more preferably below 400° C.

In yet a further embodiment, the LiMO₂ or xLi₂M′O₃.(1−x)LiMO₂ compositeelectrodes may be preconditioned by subjecting the electrodes only tothe proton-containing medium, i.e., without a reduction step. Forexample, it is already known that acid treatment of Li₂MnO₃ yields aproton-exchanged Li_(2−y)H_(y)MnO₃ compound that can be reformulated, incomponent notation, as (1−y/2)Li₂O.y/2H₂O.MnO₂. In this respect, itstands to reason that if the pH is less than 7, proton exchange willoccur in the LiMO₂ or xLi₂M′O₃.(1−x)LiMO₂ composite electrodes of theinvention, irrespective of the choice of the proton-containing solutionof an inorganic acid or organic acid, such as phosphoric acid, sulfuricacid, nitric acid, acetic acid, hydrochloric acid and hydrofluoric acid.It is believed that such an ion-exchange process followed by aheat-treatment step may be used effectively to precondition theelectrode because it should be easier to remove (or partially remove),by heating, a H₂O component from the structure rather than a Li₂Ocomponent, in order to increase the MnO₂ component in the initialelectrode and therefore its inherent electrochemical capacity. In afinal embodiment, this invention extends to include electrochemicallithium cells and batteries that employ the preconditioned LiMO₂ orcomposite xLi₂M′O₃.(1−x)MO₂ electrodes as fully described herein.

The following examples describe the principles of the invention andpossible methods of synthesizing the pre-reduced electrodes of thisinvention as contemplated by the inventors, but they are not to beconstrued as limiting examples.

EXAMPLE 1

Synthesis of LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ Electrodes

LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ powder was synthesized from LiOH.H₂O andMn_(0.33)Ni_(0.33)Co_(0.33)(OH)_(x)(x˜2) precursors. LiOH.H₂O was usedas supplied by Aldrich (98% pure). TheMn_(0.33)Ni_(0.33)Co_(0.33)(OH)_(x) precursor was prepared bycoprecipitation of the required stiochiometric amounts of metal nitratesM(NO₃)₂.xH₂O (M=Mn, Ni, and Co). After intimate mixing and grinding, thepowdered mixture was pressed into a pellet and placed in a mufflefurnace. A two-step heating procedure was used to fire the pelletaccording to the following procedure. First, a low temperaturecalcination step was performed at 480° C. for 5 hr. The pellet was thenground again and recompacted into pellet form. Second, a hightemperature sintering step was performed at 900° C. for 3 hr followed byrapid quenching of the pellet between two copper plates. The pellet wasground a final time. Samples of the resultingLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ powder were heated at either 250 or 350°C. for approximately 20 hr in a tubular furnace under flowing NH₃ gas.The X-ray diffraction patterns of the parentLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ compound and the NH₃-treatedLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ samples are shown in FIG. 1(a-c),respectively; there were no significant differences in the X-raypatterns of the untreated- and NH₃-treatedLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ sample, indicating that there were nosubstantial changes to the bulk of the electrode structure.

EXAMPLE 2

Electrochemical Evaluation of LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ Electrodes

Electrochemical evaluation of LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ andpreconditioned LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ positive electrodes wascarried out as follows. The electrodes for the lithium cell werefabricated from an intimate mixture of 84 wt % ofLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode powder, 8 wt % polyvinylidenedifluoride (PVDF) polymer binder (Kynar, Elf-Atochem), 4 wt % acetyleneblack (Cabot), and 4 wt % graphite (SFG-6, Timcal) slurried in1-methyl-2-pyrrolidinone (NMP) (Aldrich, 99+%). An electrode laminatewas cast from the slurry onto an Al current collector foil using adoctor-blade. The laminate was subsequently dried, first at 75° C. for10 h, and thereafter under vacuum at 70° C. for 12 h. The electrolytewas 1 M LiPF₆ in ethylene carbonate (EC):diethyl carbonate (DEC) (1:1mixture). The electrodes were evaluated at both room temperature and 50°C. in coin-type cells (size CR2032, Hohsen) with a lithium foil counterelectrode (FMC Corporation, Lithium Division) and a polypropyleneseparator (Celgard 2400). Cells were assembled inside a He glovebox (<5ppm, H₂O and O₂) and cycled on a Maccor Series 2000 tester undergalvanostatic mode with a constant current density of either 0.3 mA/cm²or 0.1 mA/cm².

The electrochemical voltage profiles, at the 15^(th) cycle, of lithiumcells, operated at room temperature between 4.6 and 2.0 V, with anuntreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode and a NH₃-treated(250° C.) LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode are shown in FIG. 2(a and b), respectively. It is clearly apparent that the capacitydelivered by the electrochemical cell containing the NH₃-treatedLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode is significantly superior tothat of the cell with the untreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂electrode in accordance with the principles of the invention.

The electrochemical voltage profiles, at the 15^(th) cycle, of lithiumcells, operated at 50° C. between 4.6 and 2.0 V, with an untreatedLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode and a NH₃-treatedLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode are shown in FIG. 3 (a and b),respectively. It is clearly apparent that the capacity delivered by theelectrochemical cell containing the NH₃-treated (250° C.)LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode is significantly superior tothat of the cell with the untreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂electrode in accordance with the principles of the invention. FIG. 4 (aand b) represents plots of electrode capacity vs. cycle number oflithium cells operated at room temperature between 4.6 and 2.0 V, withan untreated LiMn_(0.33)Ni_(0.33)CO_(0.33)O₂ electrode and a NH₃-treatedLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode, respectively, whereas FIG. 5(a and b) represents plots of electrode capacity vs. cycle number oflithium cells operated at room temperature between 4.45 and 2.5 V, withan untreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode and a NH₃-treatedLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode, respectively. FIG. 6 (a andb) represents plots of electrode capacity vs. cycle number of lithiumcells operated at 50° C., between 4.6 and 2.0 V, with an untreatedLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode and a NH₃-treatedLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode, respectively. These dataclearly illustrate the superior capacity delivered consistently by theNH₃-treated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrodes compared to theuntreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrodes in accordance withthe principles of this invention. Of particular note is that thecoulombic efficiency of the cells containing the NH₃-treatedLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode is notably superior to that ofthe cell containing the untreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂electrode (FIGS. 4 and 5). The NH₃ preconditioning step also increasesthe first-cycle reversible capacity of theLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrodes from 83% (unconditionedelectrode, Sample A) to 88% (preconditioned electrodes, Samples B and C)as shown in Table 1. TABLE 1 Charge/discharge capacities and reversiblecapacity (%) of the initial cycle of lithium cells with unconditioned-and preconditioned LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrodes. InitialCharge Initial Discharge Reversible Electrode Capacity (mAh/g) Capacity(mAh/g) Capacity (%) Sample A 229 191 83 Sample B 228 200 88 Sample C229 201 88

FIGS. 7 a, 7 b and 7 c (samples A-C, respectively) represent plots ofcyclic voltammograms between 4.6 and 2.0 V vs. metallic lithium of anuntreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode, aLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode treated with NH₃ at 250° C.,and a LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode treated with NH₃ at 350°C., respectively. It is significant that the second oxidative sweep ofthe untreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode between 3.5 and4.25 V (FIG. 7 a) occurs at a lower potential than the initial sweep,indicating that the surface of the electrode had been reducedelectrochemically during the first cycle. By contrast, the difference inpotential between the first and second oxidative sweep of anLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode treated with NH₃ at 250° C.(FIG. 7 b) and at 350° C. (FIG. 7 c) is less than it is for theuntreated LiMn_(0.33)Ni_(0.33)Co_(0.33)O₂ electrode (FIG. 7 a),consistent with the principles of the invention that NH₃ treatmentreduces the electrode surface to provide enhanced electrode stability asdemonstrated by the improved coulombic efficiency of the NH₃-treatedelectrodes (FIGS. 4 and 5). These data illustrate that preconditioningthe electrode produces improved cycling characteristics. Although it isdifficult to determine the precise degree to which the parent electrodeis reduced by the chemical preconditioning process, particularly at thesurface, excessive reduction will damage the electrode structure anddegrade the electrochemical properties of the electrode. It istherefore, believed that optimum electrochemical performance will onlybe achieved for mild levels of reduction, i.e., for δ less than 0.2,preferably less than 0.1 in theLi_((2+2x)/(2+x))M′_(2x/(2+x))M_((2−2x)/(2+x))O_(2−δ) electrodes of thisinvention.

EXAMPLE 3

Synthesis of 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ Composite Electrodes

An electrode material with the composite formula0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ was prepared directly fromNi_(1−x)Mn_(x)(OH)₂ and LiOH.H₂O precursors using the required Li:Mn:Niratio. The Ni_(1−x)Mn_(x)(OH)₂ precursor was prepared by precipitationfrom a basic LiOH solution of Ni(NO₃)₂ and Mn(NO₃)₂ (pH˜11). Thereagents were intimately mixed in an acetone slurry, dried in an ovenovernight, and subsequently fired at 480° C. for 12 h and then at 900°C. for 5 h in air. Thereafter, the 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂product was rapidly quenched (also in air). The X-ray diffractionpattern of the resulting powder is shown in FIG. 8 a (Sample D). Theelectrode powder was preconditioned according to the followingprocedures prior to cell assembly: 1) subjecting the powder to flowingNH₃ gas in a tubular furnace at 200° C. for approximately 20 hrs, theX-ray diffraction pattern of this product being shown in FIG. 8 b(Sample E); 2) washing the powder in de-ionized water (p˜6.5) beforesubjecting the powder to flowing NH₃ gas in a tubular furnace at 200° C.for approximately 20 hrs, the X-ray diffraction pattern of this productbeing shown in FIG. 8 c (Sample F); 3) treating the powder with 0.1 MHNO₃ (pH˜1.8) before subjecting the powder to flowing NH₃ gas in atubular furnace at 200° C. for approximately 20 hrs, the X-raydiffraction pattern of this product being shown in FIG. 8 d (Sample G).There were no significant differences in the X-ray patterns of SamplesD, E, F and G, indicating that there were no significant changes to thebulk structure of the individual compounds. Refinement of the latticeparameters of Samples D, E and G using rhombohedral symmetry (hexagonalsetting), which is typical of layered-type compounds such as LiCoO₂(Table 2), showed that there was an insignificant change of the latticeparameters after NH₃-treatment (Sample D). However, the slight expansionof the c-axis in Sample G is consistent with the removal of some lithiumfrom the composite structure as a result of acid-treatment. TABLE 2Lattice parameters of Samples D, E, and G. Electrode a (Å) c (Å) SampleD (untreated) 2.8655(3) 14.254(3) Sample E (NH₃-treated) 2.8666(3)14.259(3) Sample G (HNO₃/NH₃-treated) 2.8711(3) 14.271(4)

EXAMPLE 4

Electrochemical Evaluation of 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂Composite Electrodes

The construction of lithium cells containing0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ and preconditioned0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ positive electrodes was carried outby the same procedure as described in Example 2. Cells were cycled undergalvanostatic mode between 4.6 and 2.0 V at constant current density(0.1 mA/cm²).

The voltage profiles of the first charge/discharge cycle of lithiumcells with:

an untreated 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ electrode (Sample D);

an NH₃-treated 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ electrode (Sample E);

an H₂O/NH₃-treated 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ electrode (SampleF); and

an HNO₃/NH₃-treated 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.05)O₂ electrode(Sample G)

are shown in FIG. 9(a-d), respectively.

The capacities obtained during the first charge and discharge and thecycling efficiency of the initial cycle of these cells are provided inTable 2 and illustrated graphically in FIG. 10(a-d), respectively. TABLE3 Charge/discharge capacities and reversible capacity (%) of the initialcycle of lithium cells with 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ andpreconditioned 0.3Li₂MnO₃.0.7LiMn_(0.5)Ni_(0.5)O₂ electrodes. InitialCharge Initial Discharge Reversible Electrode Capacity (mAh/g) Capacity(mAh/g) Capacity (%) Sample D 259 203 78 Sample E 254 199 78 Sample F248 204 82 Sample G 205 195 95

The data in Table 3 demonstrate that an improvement in the irreversiblecapacity loss during the initial cycle can be obtained bypreconditioning xLi₂M′O₃.(1−x)LiMO₂ composite electrodes, particularlythose containing a Li₂MnO₃ component by subjecting the electrodes to anacidic medium, e.g., deionized water (pH˜6.5) or an HNO₃ solution(pH˜1.8) and that the improvement is significantly more pronounced whenthe electrodes are preconditioned with acid at low pH (Sample G, 95%efficiency). The excellent 95% capacity retention of electrode sample Gwhen charged to the high potential of 4.6 V vs. Li⁰ is indicative of astabilized electrode with a significantly reduced surface reactivitycompared with electrode samples D, E and F.

EXAMPLE 5

An electrode material with the formula 0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ was prepared as follows.The (Mn_(0.330)Ni_(0.335)Co_(0.335))(OH)_(x)(x˜2) precursor was preparedby coprecipitation in a similar manner to the procedure described inExample 1. Li₂CO₃ was intimately with the(Mn_(0.330)Ni_(0.335)Co_(0.335))(OH)_(x)(x˜2) precursor in a ratio ofratoi Li₂CO₃:(Mn_(0.330)Ni_(0.335)Co_(0.335))(OH)_(x)=0.55:1 (orLi:(Mn+Ni+Co)=1.1:1). The powder mixture was calcined at 700° C. for 16hours in air and then at 950° C. for 12 hours in air to make0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ (Sample H). A0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ sample was treated withan acidic 0.014M NH₄F (aqueous) solution, the pH of which was 5.54, andthereafter dried at either at 300° C. or 600° C. in air for 6 hours(Samples I and J, respectively). A0.1Li₂MnO₃.0.9LiCu_(0.372)Ni_(0.372)Mn_(0.256)O₂ sample was also treatedwith a 0.016M NH₄F solution in laboratory grade methanol containingtrace amounts of water (typically up to 0.1%), the pH of which was 6.24,and thereafter dried at 600° C. in air for 6 hours (Sample K). The X-raydiffraction patterns of Samples H, I, J and K are shown in FIG. 13(a-d).There were no significant differences in the X-ray patterns of SamplesH, I, J and K, indicating that no significant changes had occurred tothe bulk structure of the individual compounds during thepreconditioning reactions.

EXAMPLE 6

Electrochemical Evaluation of0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ Electrodes

The construction of lithium cells containing0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrodes of Example 5was carried out in a similar manner to the procedure described inExample 2. Cells were cycled galvanostatically between 4.6 and 3.0 V atconstant current density (first two cycles at 0.1 mA/cm² and followingcycles at 0.5 mA/cm²).

The voltage profiles of the first charge/discharge cycle of lithiumcells with an untreated 0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂electrode; a 0.1 Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrodetreated with an acidic NH₄F solution (aqueous) and dried at 300° C.; a0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode treated withan acidic NH₄F solution (aqueous) and subsequently dried at 600° C.; anda 0.1 Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrode treatedwith an acidic NH₄F solution (methanol+trace H₂O) and subsequently driedat 600° C. are shown in FIG. 14(a-d), respectively. The capacitiesobtained during the first charge and discharge and the cyclingefficiency of the initial cycle of these cells are provided in Table 4;the cycling stability of the untreated electrode and preconditionedelectrodes is shown graphically in the capacity vs. cycle number plots(30 cycles) in FIG. 15. TABLE 4 Charge/discharge capacities andreversible capacity (%) of the initial cycle of lithium cells with0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ and preconditioned0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂ electrodes. InitialCharge Initial Discharge Reversible Electrode Capacity (mAh/g) Capacity(mAh/g) Capacity (%) Sample H 230 184 80.1 Sample I 230 194 84.4 SampleJ 233 197 84.5 Sample K 228 189 83.3

The electrochemical data of Example 6 are fully consistent with theprinciples of this invention. The data demonstrate that whenxLi₂M′O₃.(1−x)LiMO₂ (0≦x<1) electrodes, as represented by 0.1Li₂MnO₃.0.9LiCo_(0.372)Ni_(0.372)Mn_(0.256)O₂, are chemicallypreconditioned prior to cell assembly in a proton-containing, acidicsolution with a pH<7.0, the capacity, cycling efficiency and cyclingstability of lithium cells, when charged to high potentials, areimproved. For example, the improved coulombic efficiencies of theinitial charge/discharge cycle of cells with preconditioned electrodesSamples I, J, and K (83.3-84.5%) when charged to the high potential of4.6 V vs. Li⁰ are indicative of stabilized electrodes with reducedsurface reactivity compared to that of the untreated control sample H(80.1%). Furthermore, the capacity vs. cycling plots in FIG. 15 provideunequivocal evidence that higher electrochemical capacities can beobtained from acid-treated electrodes Samples I, J and K on cycling and,moreover, that improved cycling stability can be achieved by usingacidic media in which the salt of a relatively strong acid and arelatively weak base, such as NH₄F, is dissolved in a non-aqueoussolvent such as an alcohol, for example, methanol, as in Sample K. Inthis respect, it should be noted that alcohols are readily miscible withwater, and therefore are likely to contain trace amounts of H₂O, evenwhen in high purity form. Because of the miscibility of water withnon-aqueous solvents such as methanol, ethanol, or the like, ittherefore stands to reason and is obvious to those skilled in the artthat the amount of water in such co-solvents can be tailored to controlthe pH of the acid solution (pH<7) for the purposes of this invention.The invention therefore includes using acidic solutions of saltsdissolved in one or more aqueous or non-aqueous solvents, such asammonium salts NH₄NO₃, NH₄C₁, NH₄F, and NH₄HF₂ (NH₄F.HF) dissolved inmethanol, ethanol, or the like, to provide acidic solutions having apH<7.0, to precondition the electrodes and prior to heating theelectrodes above 100° C., but preferably below 600° C., in order tocompletely dry the electrodes and to stabilize the electrode surface aseffectively as possible.

Although the precise reasons for the improved electrochemical behaviorof Samples I, J and K over Sample H are not yet fully understood, theapplicants believe that amongst the major reasons for the improvedbehavior brought about by the preconditioning reactions are: 1) agreater stability of the preconditioned electrode surface, 2) possibleH⁺—Li⁺ ion-exchange reactions and 3) a removal of some lithia (Li₂O)from the xLi₂M′O₃ component of the electrode structure, as describedhereinbefore. It is also well known that NH₃ or NH₄-bearing species canact as reducing agents, and therefore that reduction of the electrodesurface can occur, particularly when the electrodes are dried atelevated temperatures. Moreover, when acids such as HNO₃, HCl and HF areused, then the replacement of divalent surface oxygen ions, O²⁻, bymonovalent NO₃ ⁻, Cl⁻ or F⁻ ions would have the effect of reducing thenearest neighbor transition metal ions (M and M′) of thexLi₂M′O₃.(1−x)LiMO₂ (0≦x<1) electrode structure. In this respect,transition metal oxy-nitrato, oxychloride and oxyfluoride compounds arealready known to exist, such as FeONO₃, TiO(NO₃)₂, FeOCl, FeOF, VOCl₂and VOF, and it is therefore believed that such oxy-nitrato-,oxychloride- and oxyfluoride species may form at least at the electrodesurfaces of this invention, thereby imparting greater structuralstability to these surfaces and reducing the reactivity of the electrodesurfaces towards the electrolyte at high potentials, typically above 4.2or 4.3 V. The same principles may also apply, in likewise fashion, toother inorganic acids and organic acids, such as phosphoric acid,sulfuric acid and acetic acid.

The examples and results of this invention demonstrate that improvedelectrochemical performance of layered lithium metal oxide electrodes asdefined herein, can be significantly improved by preconditioning theelectrodes either with a reducing agent such as ammonia or by acidtreatment or a combination thereof, particularly when the electrodes aresubjected to high potentials in excess of 4.2 V during charge. Thisinvention, therefore, also relates to non-aqueous electrochemicallithium cells containing such preconditioned positive electrodes, atypical cell shown schematically in FIG. 11, represented by the numeral10 having a negative electrode 12 separated from a positive electrode 16by an electrolyte 14, all contained in an insulating housing 18 withsuitable terminals (not shown) being provided in electronic contact withthe negative electrode 12 and the positive electrode 16. Binders andother materials normally associated with both the electrolyte and thenegative and positive electrodes are well known in the art and are notfully described herein, but are included as is understood by those ofordinary skill in this art. FIG. 12 shows a schematic illustration ofone example of a battery in which two strings of electrochemical lithiumcells, described above, are arranged in parallel, each string comprisingthree cells arranged in series. The invention also includes methods ofmaking the preconditioned positive electrodes, cells and batteriesincluding same,

While there has been disclosed what is considered to be the preferredembodiments of the present invention, it is understood that variouschanges in the details may be made without departing from the spirit, orsacrificing any of the advantages of the present invention and thatadditional improvements in the capacity and stability of the electrodescan be expected to be made in the future by improving and optimizing theprocessing techniques whereby lithium metal oxide electrodes arechemically preconditioned either by acid treatment or reductionprocesses, or a combination thereof, prior to the construction ofelectrochemical lithium cells.

1. An electrode for a non-aqueous lithium cell, comprising a lithiummetal oxide having the formula xLi₂M′O₃.(1−x)LiMO₂, in which 0≦x<1, andin which M is a non-lithium metal ion with an average trivalentoxidation state selected from two or more first-row transition metals orlighter metal elements in the periodic table, and M′ is one or more ionswith an average tetravalent oxidation state selected from the first- andsecond-row transition metal elements and Sn, the electrodes beingpreconditioned in a proton-containing medium with a pH<7.0 including oneor more of phosphoric acid, sulfuric acid, nitric acid, acetic acid,hydrochloric acid or hydrofluoric acid.
 2. The electrode of claim 1, inwhich M is selected from Co, Ni, Mn, Ti, Mg and Al, and M′ is selectedfrom Ti, Mn, Zr, Ru and Sn.
 3. The electrode of claim 2, in which M isselected from Co, Ni and Mn, and M′ is selected from Ti and Mn.
 4. Theelectrode of claim 3, in which M is selected from Co, Ni and Mn, and M′is selected from Mn.
 5. The electrode of claim 4, in which M is selectedfrom Ni and Mn, and M′ is selected from Mn.
 6. A method of synthesizingthe electrode of claim 1 by subjecting the xLi₂M′O₃.(1−x)LiMO₂ electrodeto an acidic solution with pH<7.0, and thereafter heating the electrodein air above 100° C.
 7. The method according to claim 6 in which theelectrode is heated below 600° C.
 8. The method according to claim 7 inwhich the electrode is heated below 400° C.
 9. The method according toclaim 6 in which the proton-containing medium consists of de-ionizedwater and one or more of an inorganic acid.
 10. An electrode madeaccording to the method of claim
 6. 11. A method of synthesizing theelectrode of claim 1 by subjecting the xLi₂M′O₃.(1−x)LiMO₂ electrode toan acidic solution with pH<7.0, containing an ammonium salt dissolved inone or more aqueous or non-aqueous solvents and thereafter heating theelectrode in air above 100° C.
 12. The method of claim 11, in which theacidic solution is NH₄F or NH₄HF₂ dissolved in water or an alcohol. 13.The method of claim 12, in which the NH₄F salt is dissolved in methanol.14. The method of claim 13, in which the NH₄F salt is dissolved inmethanol and thereafter heating the electrode in air at 600° C.
 15. Anelectrode made according to the method of claim
 11. 16. A non-aqueouslithium electrochemical cell comprising a negative electrode, anelectrolyte and an uncycled positive electrode comprising a lithiummetal oxide having the formula xLi₂M′O₃.(1−x)LiMO₂, in which 0≦x<1, andin which M is a non-lithium metal ion with an average trivalentoxidation state selected from two or more first-row transition metals orlighter metal elements in the periodic table, and M′ is one or more ionswith an average tetravalent oxidation state selected from the first- andsecond-row transition metal elements and Sn, said positive electrodebeing preconditioned in a proton-containing medium with a pH<7.0containing an inorganic acid.
 17. A non-aqueous lithium batterycomprising a plurality of electrically connected electrochemical cells,each cell having a negative electrode, an electrolyte and an uncycledpositive electrode comprising a lithium metal oxide having the formulaxLi₂M′O₃.(1−x)LiMO₂, in which 0≦x<1, and in which M is a non-lithiummetal ion with an average trivalent oxidation state selected from two ormore first-row transition metals or lighter metal elements in theperiodic table, and M′ is one or more ions with an average tetravalentoxidation state selected from the first- and second-row transition metalelements and Sn, said positive electrode being preconditioned in aproton-containing medium with a pH<7.0 containing an inorganic acid. 18.The electrode of claim 1, wherein said proton-containing solutioncontains fluoride ions.
 19. The non-aqueous lithium electrochemical cellof claim 16, wherein said proton-containing medium contains fluorideions.
 20. The non-aqueous lithium battery of claim 17, wherein saidproton-containing medium contains fluoride ions.